Fabrication of superamphiphobic-textured surfaces with reversibly switchable wettability

To realize switchable wettability for water and oils, we firstly design a facile approach to achieve superamphiphobic-textured surfaces that display the apparent contact angles greater than 150° and the sliding angles smaller than 10° for various liquids, such as water and hexadecane. Then, plasma treatment and surface fluorination were performed on the superamphiphobic surface. The tunability of the chemical composition, along with hierarchical rough surface structure, gave rise to reversibly switchable wettability between superamphiphobicity and superamphiphilicity. The wettability of the textured surface was demonstrated by visible experimental results and measurements. The reason of switchable wettability can be confirmed by X-ray photoelectron spectroscopy analysis. These results give a useful attempt in simultaneously and reversibly switching wettability for water and oils, which may have potential application in functional superamphiphobic materials.     

A methodology for fabrication of thermomechanically activated switchable surface wettability

In this study a platform is laid out for the creation of a multitiered surface exhibiting switchable wettability. This is done through a combination of both an acrylate‐based polymer understructure photopolymerized into a pillared array, and selectively placed surface treatments on these pillars. The acrylate‐based polymer is created through a systematic study and is shown to exhibit drastic alterations in material stiffness over a 19 °C temperature transition under aqueous conditions, allowing for stiff, erect pillars in the low temperature state, and pliable pillars that can easily be bent in the high temperature state. The glass transition temperature and onset temperature for the polymer system is found to be 49 and 30 °C, respectively. Three different surface treatments, including trichloro(1H,1H,2H,2H‐perfluorooctyl)silane, polydimethylsiloxane, and polydopamine, are investigated using static contact angle studies, and are selectively deposited onto the pillared surface such that a hydrophobic surface is exposed with the pillars erect, and a hydrophilic surface is exposed with the pillars in the bent state. The surface is shown to transition between first a hydrophobic, then hydrophilic state and return to a hydrophobic state when the investigations are coupled together forming a hierarchical surface structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44122.     

Doubly thermo-responsive brush-linear diblock copolymers and formation of core-shell-corona micelles

Doubly thermo-responsive brush-linear diblock copolymer of poly[poly(ethylene glycol) methyl ether vinylphenyl]-block-poly(N-isopropylacrylamide) (PmPEGV-b-PNIPAM) is prepared by RAFT polymerization. The obtained brush-linear diblock copolymer exhibits two lower critical solution temperatures (LCSTs) corresponding to the linear poly(N-isopropylacrylamide) (PNIPAM) block and the brush poly[poly(ethylene glycol) methyl ether vinylphenyl] (PmPEGV) block in water. This brush-linear diblock copolymer undergoes a two-step temperature sensitive micellization. At temperature above the first LCST, the brush-linear diblock copolymer self-assembles into core-corona micelles with the dehydrated PNIPAM block forming the core and the solvated brush PmPEGV block forming the corona. When temperature increases above the second LCST, the polystyrene backbone in the brush PmPEGV block collapses onto the dehydrated PNIPAM core to form core-shell-corona micelles, in which the dehydrated PNIPAM block forms the core, the collapsed polystyrene backbone in the brush PmPEGV block forms the shell and the solvated poly(ethylene glycol) side-chains forms the corona. The effect of the length of the PNIPAM block and the length of the poly(ethylene glycol) side-chains on the thermo-responsive micellization and the size of core-shell-corona micelles is investigated.     

Thermo-responsive behavior of hybrid core cross-linked polymer micelles with biocompatible shells

Poly(2-(methacryloyloxy)ethyl phosphorylcholine)-b-poly(N-isopropylacrylamide-co-2-(N,N-dimethylamino)ethyl methacrylate) (pMPC-b-p(NIPAM/DMA)) was synthesized via reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization. Below the critical aggregation temperature (CAT), i.e., about 40 °C, the diblock copolymer dissolved in water as a unimer with a hydrodynamic radius (R_h) of ca. 10 nm. Above CAT the diblock copolymers formed polymer micelles with an R_h of ca. 40 nm, composed of a p(NIPAM/DMA) core and biocompatible pMPC shell due to hydrophobic self-aggregation of the thermo-responsive p(NIPAM/DMA) block. The pendent 2-(N,N-dimethylamino)ethyl group of DMA in pMPC-b-p(NIPAM/DMA) reduced HAuCl₄ to form gold nanoparticles (AuNPs) and could attach to their surfaces. The cores of these polymer micelles could be cross-linked above CAT by HAuCl₄, which upon being reduced generated AuNPs as cross-linking points to form core cross-linked (CCL) polymer micelles, as confirmed by UV-vis absorption and dynamic light scattering measurements. The CCL polymer micelles absorbed visible light at 532 nm because of surface plasmon resonances of the AuNPs. The R_h of the CCL polymer micelles remained at ca. 40 nm regardless of temperature.     

Synthesis and characterization of brush copolymers based on methoxy poly(ethylene glycol) and poly(ε‐caprolactone)

Brush copolymers composed of methoxy poly(ethylene glycol) (MPEG) and poly(ε‐caprolactone) (PCL) have been synthesized by the ring‐opening polymerization of ε‐caprolactone initiated by hydroxyl function of thermally esterified MPEG‐citrate in presence of stannous octoate. Citric acid (CA) acts as spacer between brush‐like MPEG and the long chain of PCL. Existence of hydrophobic domains as cores of the micelles were characterized by ¹H NMR spectroscopy and further confirmed with fluorescence technique using pyrene as a probe. Critical micelle concentration (CMC) of the synthesized copolymer decreased from 0.019 to 0.0031 mg/mL on increasing the fraction of PCL. Along with the physicochemical study, the brush copolymers were explored for the preparation of nanoparticles by nanoprecipitation technique. The morphology and geometry of micelles were investigated by using DLS, AFM, and TEM. Hydrodyanamic dimensions of micelles were around 118 and 178 nm with the core size of 8–10 nm, which further aggregated to form secondary micelle of 60–90 nm. Such assembled polymeric micelles with its flexible dendritic MPEG corona could hold a promise for the immobilization (encapsulation) of hydrophobic drugs and subsequently promote sustained release so that it can be a good vehicle for anti‐cancer drug deliverance. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Switching surface wettability properties

In this work, recent developments regarding design and preparation of surfaces to modify their wettability behavior by switching between the superhydrophobic and the superhydrophilic state under physical and chemical stimuli are summarized. The complex systems and the strategies developed in nature are investigated as a fundamental support considering the potential applications of these two ‘superstates’ in basic research and in a range of industrial fields, adapting these properties for engineering new and efficient devices or improving existent techniques.     

The effect of side chains on the reactive rate and surface wettability of pentablock copolymers by ATRP

The reactive rate and surface wettability of three pentablock copolymers PDMS‐b‐(PMMA‐b‐PR)₂ (R = 3FMA, 12FMA, and MPS) obtained via ATRP for coatings are discussed. Poly(dimethylsiloxane) (PDMS) is used as difunctional macroinitiator, poly(methyl methacrylate) (PMMA) as the middle block, while poly(trifluoroethyl methacrylate) (P3FMA), poly(dodecafluoroheptyl methacrylate) (P12FMA) and poly(3‐(trimethoxysilyl)propyl methacrylate) (PMPS) as the end block, respectively. Their reactive rates obtained by gas chromatography (GC) analysis indicate that 3FMA gains 8.053 × 10^?5 s^?1 reactive rate and 75% conversion, higher than 12FMA (4.417 × 10^?5 s^?1, 35%), but MPS has 1.9389 × 10^?4 s^?1 reactive rate and 96% conversion. The wettability of pentablock copolymer films is characterized by water contact angles (WCA) and hexadecane contact angles (HCA). The PDMS‐b‐(PMMA‐b‐P12FMA)₂ film behaves much higher advancing and receding WAC (120° and 116°) and HCA (60° and 56°) than PDMS‐b‐(PMMA‐b‐P3FMA)₂ film (110° and 106° for WAC, 38° and 32° for HAC) because of its fluorine‐rich surface (20.9 wt % F). However, PDMS‐b‐(PMMA‐b‐PMPS)₂ film obtains 8° hysteretic contact angle in WAC (114°–106°) and HAC (32°–24°) due to its higher surface roughness (138 nm). Therefore, the fluorine‐rich and higher roughness surface could produce the lower water and oil wettability, but silicon‐rich surface will produce lower water wettability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40209.     

Association behavior of thermo-responsive block copolymers based on poly(vinyl ethers)

Thermo-sensitive nanosized structures have been prepared in water from poly(methyl vinyl ether)-block-poly(isobutyl vinyl ether) (PMVE-b-PIBVE) block copolymers. The composition and the architecture (diblock and triblock architectures) of the PMVE-b-PIBVE copolymers have been varied. The investigated copolymers had an asymmetric composition with a major PMVE block. While the PIBVE blocks are hydrophobic, the PMVE blocks are hydrophilic at room temperature and become hydrophobic above their demixing temperature (around 36 °C) as a result of the lower critical solution temperature (LCST) behavior. At room temperature, the amphiphilic copolymers aggregate in water above a critical micelle concentration, which has been experimentally measured by hydrophobic dye solubilization. The hydrodynamic diameter of the structures formed above the cmc has been measured by dynamic light scattering (DLS) while their morphology has been studied by transmission electron microscopy (TEM). ¹H NMR measurements in D₂O at room temperature reveal that the aggregates contain PIBVE insoluble regions surrounded by solvated PMVE chains. These investigations have shown that polydisperse spherical micelles are formed for asymmetric PMVE-b-PIBVE copolymers containing at least 9 IBVE units. For copolymers containing less IBVE units, loose aggregates are formed.Finally, the thermo-responsive, reversible properties of these structures have been investigated. Above the cloud point of the copolymers, the loose aggregates precipitate while the micelles form large spherical structures.     

Self-assembly of well-defined thermo-responsive fluoropolymer and its application in tunable wettability surface

A facile and effective strategy for fabricating a tunable wettability surface on cotton fabrics by dip-coating into self-assembled fluoro-copolymer micelle of poly(hexafluorobutyl methacrylate)-b-poly(oligo(ethylene glycol) methyl ether methacrylate) is developed. The micelle solution, exhibiting thermal-responsive property with uniform spheres at 20 °C and irregular particles at above 50 °C, shows switchable wetting behaviors at different dipping and drying temperatures due to the changeable chemical structure of responsive polymer on fibers. The cotton fabric processed in cold micelle is smooth caused by the self-assembled structure of thermal-responsive micelle with fluorinated parts on the outmost fiber-layer, and it also has high fluorine content and good hydrophobic property. While the one treated in hot micelle is rough, and has good hydrophilic property due to the outmost layer of hydrophilic PEG segments on fibers. This work provides a simple strategy to construct controllable wettability surface and makes a great application potential in household commodity, industrial products and other smart complex materials.     

AM/NIPAM对P(NIPAM-co-AM)温敏凝胶性能影响

以丙烯酰胺(AM)、N-异丙基丙烯酰胺(NIPAM)为单体,过硫酸铵(APS)-亚硫酸氢钠(SBS)为氧化-还原引发体系,N,N'-亚甲基双丙烯酰胺(BIS)为交联剂,制备了亲水型温敏凝胶P(NIPAM-co-AM)。研究了投料比AM/NIPAM对凝胶性能的影响。结果表明：随着凝胶体系中亲水单体AM比例的增大,共聚凝胶溶胀率、保水率、硬度均提高。当AM从0增大到100%时,凝胶硬度从84.929g增为1255.222g。DSC表明,当AM含量从2%提高到10%时,凝胶LCST从38.61℃增加到57.95℃。随着AM比例降低,凝胶LCST向低温方向移动,相变范围温敏性越好。     

Control of wettability of polymers using organic surface chemistry

The analytical technique of contact angle analysis has been used both to monitor organic transformations on the surfaces of fluoropolymer films and also to help correlate surface structure with wettability. This paper describes the preparation and characterization, particularly with regard to wettability, of several series of surface-modified derivatives of chemically resistant polymers. A series of esters prepared with acid chlorides and alcohol-functionalized poly(chlorotrifluoroethylene) (PCTFE-OH) displays expected water contact angle trends and indicates that wettability can be controlled using organic surface chemistry. The identification of carboxylic acids on the surface of poly(vinylidene fluoride) (PVF₂-CO₂H) by the pH dependence of the water contact angle is discussed. Also described and compared with X-ray photoelectron spectroscopy is the use of contact angle for observing polymer surface reconstruction.     

偶联剂对竹材表面润湿性及胶合强度的影响

利用3种硅烷偶联剂KH550、KH560及KH602和1种偶联剂HMR处理竹材表面,考查了偶联剂对竹材表面性能及粘接性能的影响。结果显示,偶联剂HMR、KH560及KH602可以提高竹片的表面自由能,改善竹片的表面润湿性能;而KH550处理竹片后降低了竹片的表面自由能,竹片的表面润湿性变差。但是4种偶联剂均能提高竹片的胶合强度。综合价格与性能因素,偶联剂HMR的使用效果最好。     

口气清新的牙膏和牙刷市场

对我国经济的增长及牙膏的消费情况进行了概述。目前,口腔护理品作为美容产品而非化妆品占据市场,而中国中低收入的消费者占消费品市场的90％以上,这一消费群体占据着牙膏消费市场的很大一部分。介绍了目前牙膏中所使用的能提高口腔清洁效果的新型研磨剂。强调了清洁口腔和口腔护理的重要性。     

Effect of solvent on surface wettability of electrospun polyphosphazene nanofibers

Two kinds of biodegradable polymers, poly(ε‐caprolactone) (PCL) and poly[(alanino ethyl ester)_0.67 (glycino ethyl ester)_0.33 phosphazene] (PAGP), were electrospun by using four different solvents. All PCL nanofibrous mats had similar surface water contact angles independent of solvents. However, it was found that the water contact angles of PAGP nanofibrous mats were 102.2° ± 2.3°, 113.5° ± 2.2°, 115.8° ± 1.4°, and 119.1° ± 0.7°, respectively, when trifluoroethanol, chloroform, dichloromethane, and tetrahydrofuran were used as a solvent. This difference was supposed mainly due to phosphorous and nitrous atoms in PAGP being dragged to fiber surface with solvent evaporation during the solidification of nanofibers, because of the strong interaction between positive phosphorous atoms and electronegative atoms in solvents. This interaction was confirmed by Fourier Transform Infrared, and the accumulation of phosphorous and nitrous atoms in the solvent‐casting PAGP film surface was identified by X‐ray photoelectron spectrometry analysis. PCL samples did not show the solvent‐controlled surface wettability because it contained fewer polar atoms. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

十四酸铜超疏水表面的溶剂热法制备及其润湿性

超疏水表面是防止低温条件下风机叶片表面结冰、保证机组安全运行的重要材料之一。本文以十四酸乙醇溶液和铜片为前体,基于溶剂热法将十四酸铜原位生长于铜片表面,通过调控前体浓度和反应时间获得了不同润湿性的疏水表面,实现了疏水表面润湿性的有效调控。此外,采用扫描电子显微镜（SEM）观察了十四酸铜团簇的微结构及分布状态;借助X射线衍射仪（XRD）验证团簇粉末的晶格成分;通过接触角测量仪量化不同条件下样品的表面润湿性。结果表明,随着铜片表面十四酸铜团簇密集程度的增加,液滴与铜片的接触角增大,铜片润湿性降低;十四酸乙醇溶液浓度及反应时间可以显著改变十四酸铜分布状态,进而改变表面润湿性。疏水表面润湿性的变化是由于Ostwald熟化促进晶体生长,使表面的“禾苗”状聚合物逐渐生长成十四酸铜微米花。     

Application of thermo-responsive poly(methyl vinyl ether) containing copolymers in combination with ultrasonic treatment for pigment surface modification in pigment dispersions

The process of surface modification of hydrophobic organic (copper phthalocyanine (CuPc)) as well as hydrophilic inorganic pigments (titanium dioxide) in aqueous dispersions by employing tailor-made thermo-responsive copolymers and the colloidal stability have been studied as a function of temperature. The pigment surface modification is achieved by conventional adsorption and by thermoprecipitation of amphiphilic methyl vinyl ether (MVE) containing block and graft copolymers, exhibiting a lower critical solution temperature (LCST), with poly(isobutyl vinyl ether) blocks and poly(ethylene oxide) side chains, respectively. The effect of mechanical treatment of the pigment dispersion by ultrasonic power alone or in combination with the LCST property was investigated. The course of the pigment surface coating process was followed by the electrokinetic sonic amplitude (ESA) method. The temperature-controlled sorption of PMVE-g-PEO graft copolymers on both inorganic and organic pigment surfaces was investigated. It was found that ultrasonic treatment together with LCST thermoprecipitation is a promising method for the surface modification of pigments with regard to dispersion stability.     

含氟丙烯酸酯共聚物涂膜表面润湿性的研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸β–羟乙酯(HEMA)、(甲基)丙烯酸高级酯(AAs)、含氟(甲基)丙烯酸酯(Fs)等单体为原料,HDI三聚体为固化剂,通过改变共聚物组成、氟碳链长、(甲基)丙烯酸高级酯烷烃链长等因素,合成了一系列的含氟丙烯酸酯共聚物。采用水、煤油和液压油接触角以及水滴滚动距离,表征了共聚物涂膜的表面润湿性,并探讨了其影响因素。结果表明,共聚物组成和结构、烷烃链长对水的接触角影响不大,而对水的滚动性能具有较大影响;氟碳链长以及氟单体的添加方式对油水接触角和水的滚动性能有较大影响;烷烃侧链的柔顺性对油的接触角影响较大,而对水几乎没有影响。     

Effect of surface curvature and wettability on nucleation of methane hydrate

Natural gas hydrate nucleation is a complex physical and chemical process that is not well understood presently. In this article, an improved thermodynamic model is proposed to analyze the effects of surface curvature and wettability on methane hydrate nucleation for the first time. The results indicate that methane hydrate nucleation is more difficult on hydrophilic curvature surfaces under the same conditions, with a larger critical nucleation radius and required energy barrier than on hydrophobic surfaces. Furthermore, a convex surface is more favorable for forming methane hydrate under the same conditions than a concave surface. The model's results are critical in elucidating the microscopic mechanism of methane hydrate nucleation and providing a theoretical foundation for developing technologies for strengthening and inhibiting hydrate formation.     

Preparation of pH-responsive membranes with amphiphilic copolymers by surface segregation method☆

Novel pH-responsive membranes were prepared by blending pH-responsive amphiphilic copolymers with pol-yethersulfone (PES) via a nonsolvent-induced phase separation (NIPS) technique. The amphiphilic copolymers bearing Pluronic F127 and poly(methacrylic acid) (PMAA) segments, abbreviated as PMAAn–F127–PMAAn, were synthesized by free radical polymerization. The physical and chemical properties of the blend membranes were evaluated by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectrum, water con-tact angle, Zeta potential and X-ray photoelectron spectroscopy (XPS). The enrichment of hydrophilic PMAA seg-ments on the membrane surfaces was attributed to surface segregation during the membrane preparation process. The blend membranes had significant pH-responsive properties due to the conformational changes of surface-segregated PMAA segments under different pH values of feed solutions. Fluxes of the blend membranes were larger at low pH values of feed solutions than that at high pH values. The pH-responsive ability of the mem-branes was enhanced with the increase of the degree of PMAA near-surface coverage.